Fungicide active substance combinations

ABSTRACT

The novel active compound combinations consisting of a halogeno-benzimidazole of the formula                    
     in which 
     Z represents chlorine or bromine, 
     and the active compound groups (1) to (25) listed in the description have very good fungicidal properties.

This application is a 371 of PCT/EP98/01987, filed Apr. 6, 1998.

The present invention relates to novel active compound combinationswhich comprise known halogeno-benzimidazoles and further knownfungicidally active compounds, and which are highly suitable forcontrolling phytopathogenic fungi.

It is already known that1-(3,5-dimethyl-soxazole4-sulphonyl)-2-bromo-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzidazoleand1-(3,5-dimethyl-isoxaole4-sulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimidazolehave fungicidal properties (cf WO 97-06171). The activity of thesecompounds is good; however, at low application rates it is in some casesnot satisfactory.

Furthermore, it is already known that a large number of triazolederivatives, aniline derivatives, dicarboxirnides and other heterocyclescan be employed for controlling fungi (cf. EP-A 0 040 345, DE-A 2 201063, DE-A 2 324 010, Pesticide Manual, 9th Edition (1991), pages 249 and827, EP-A 0 382 375 and EP-A 0 515 901). Likewise, the activity of thesecompounds is not always satisfactory at low application rates.

Finally, it is also known that1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidineimine can beused for controlling animal pests such as insects (cf. Pesticide Manual,9th Edition (1991), page 491). However, fungicidal properties have nothitherto been described for this compound.

It has now been found that the novel active compound combinationsconsisting of a halogeno-benzuimdazole of the formula

in which

Z represents chlorine or bromine, and

(1) a triazole derivative of the formula

 in which

X represents chlorine or phenyl, and

Y represents

and/or

(2) the triazole derivative of the formula

and/or

(3) an aniline derivative of the formula

 in which

R¹ represents hydrogen or methyl,

and/or

(4)N-[1-(4-chlorophenyl)-ethyl]-2,2-dichloro-1-ethyl-3-methyl-cyclopropanecarboxamideof the formula

and/or

(5) the zinc propylene-1,2-bis(dithiocarbamidate) of the formula

and/or

(6) at least one thiocarbamate of the formula

Me=Zn or Mn or a mixture of Zn and Mn

and/or

(7) the aniline derivative of the formula

and/or

(8) the compound of the formula

and/or

(9) the benzothiadiazole derivative of the formula

and/or

(10) the8-t-butyl-2-(N-ethyl-N-n-propyl-amino)-methyl-1,4-dioxaspiro[5,4]-decaneof the formula

and/or

(11) the compound of the formula

and/or

(12) the compound of the formula

and/or

(13) the compound of the formula

and/or

(14) the cyanooxime derivative of the formula

and/or

(15) a pyrimidine derivative of the formula

 in which

R² represents methyl or cyclopropyl,

and/or

(16) the aniline derivative of the formula

and/or

(17) the morpholine derivative of the formula

and/or

(18) the phthalimide derivative of the formula

and/or

(19) the phosphorus compound of the formula

and/or

(20) the hydroxyethyl-triazole dervative of the formula

and/or

(21) the 1-[(6-chloro-3-pyridinyl)-methyl]-N-nitro-2-imidazolidineirnineof the formula

and/or

(22) the oxazolidinedione of the formula

and/or

(23) the benzamide derivative of the formula

and/or

(24) a guanidine derivative of the formula

 in which

m represents integers from 0 to 5 and

R³ represents hydrogen (7 to 23%) or the radical of the formula

and/or

(25) the triazole derivative of the formula

have very good fungicidal properties.

Surprisingly, the fungicidal activity of the active compoundcombinations according to the invention is considerably higher than thesum of the activities of the individual active compounds. Thus, anunforeseeable, true synergistic effect is present, and not just anaddition of activities.

The formula (I) includes

the1-(3,5-dimethyl-isoxazole4sulphonyl)-2-bromo-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimidazoleof the formula

and

the1-(3,5-dimethyl-isoxazole-4-sulphonyl)-2-chloro-6,6-difluoro-[1,3]-dioxolo-[4,5f]-benzimnidazoleof the formula

The halogeno-benzimidazoles of the formulae (Ia) and (lb) are known (cfWO 97-06171).

The formula (II) includes the compounds

1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-one ofthe formula

1-(4-chloro-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ole ofthe formula

and

1-(4-phenyl-phenoxy)-3,3-dimethyl-1-(1,2,4-triazol-1-yl)-butan-2-ole ofthe formula

The formula (IV) includes the aniline derivatives of the formulae

and

It is evident from the formula for the active compound of the formula(V) that the compound has three asymmetrically substituted carbon atoms.The product may therefore be present as a mixture of various isomers, orelse in the form of a single component. Particular preference is givento the compounds

N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1S)-2,2-dichloro-1-ethyl-3t-methyl-1r-cyclo-propanecarboxamideof the formula

and

N-(R)-[1-(4-chloro-phenyl)-ethyl]-(1R)-2,2-dichloro-1-ethyl-3t-methyl-1r-cyclo-propanecarboxamideof the formula

The formula (VII) includes the compounds

The formula (XVI) includes the compounds

The hydroxyethyl-triazole derivative of the formula (XXI) can be presentin the “thiono” form of the formula

or in the tautomeric “mercapto” form of the formula

For the sake of simplicity, only the “thiono” form is given in eachcase.

The guanidine derivative of the formula (XXV) is a substance mixture ofthe common name guazatine.

The components which are present in the active compound combinationsaccording to the invention in addition to a halogeno-benzimidazole ofthe formula (I) are also known. Specifically, the active compounds aredescribed in the following publications:

(1) Compounds of the formula (II)

DE-A2201 063

DE-A 2 324 010

(2) Compound of the formula (III)

EP-A 0 040 345

(3) Compounds of the formula (IV)

Pesticide Manual, 9th Edition (1991), pages 249 and 827

(4) Compound of the formula (V) and individual derivatives thereof

EP-A 0 341 475

(5) Compound of the formula (VI)

Pesticide Manual, 9th Edition (1991), page 726

(6) Compounds of the formula (VII)

Pesticide Manual, 9th Edition (1991), pages 529, 531 and 866

(7) Compound of the formula (VII)

EP-A 0 339 418

(8) Compound of the formula (IX)

EP-A 0 472 996

(9) Compound of the formula (X)

EP-A 0 313 512

(10) Compound of the formula (XI)

EP-A 0281 842

(11) Compound of the formula (XII)

EP-A 0 382 375

(12) Compound of the formula (XIII)

EP-A03515901

(13) Compound of the formula (XIV)

DE-A 196 02 095

(14) Compound of the formula (XV)

Pesticide Manual, 9th edition (1991), page 206

(15) Compounds of the formula (XVI)

EP-A 0270 111

EP-A 0310 550

(16) Compound of the formula (XVI)

Pesticide Manual, 9th Edition (1991), page 554

(17) Compound of the formula (XVIII)

EP-A 0 219 756

(18) Compound of the formula (XIX)

Pesticide Manual, 9th Edition (1991), page 431

(19) Compound of the formula (XX)

Pesticide Manual, 9h Edition (1991), page 443

(20) Compound of the formula (XXI)

WO 96-16048

(21) Compound of the formula (XXII)

Pesticide Manual, 9th Edition (1991), page 491

(22) Compound of the formula (XXIII)

EP-A 0393 911

(23) Compound of the formula (XXIV)

EP-A 0 600 629

(24) Substance of the formula (XXV)

Pesticide Manual, 9th Edition (1991), page 461

(25) Compound of the formula (XXVI)

Pesticide Manual, 9th Edition (1991), page 654

In addition to an active compound of the formula (I), the activecompound combinations according to the invention comprise at least oneactive compound of the compounds of groups (I) to (25). Additionally,they may comprise furtherer fungicidally active components.

The synergistic effect is particularly pronounced when the activecompounds in the active compound combinations according to the inventionare present in certain weight ratios. However, the weight ratios of theactive compounds in the active compound combinations can be variedwithin a relatively wide range. In general,

0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, ofactive compound of group (1),

0.1 to 20 parts by weight, preferably 0.2 to 10 parts by weight, ofactive compound of group (2),

1 to 150 parts by weight, preferably 1 to 100 parts by weight, of activecompound of group (3),

0.11 to 1 parts by weight, preferably 0.2 to 5 parts by weight, ofactive compound of group (4),

1 to 150 parts by weight, preferably 5 to 100 parts by weight, of activecompound of group (5),

1 to 150 parts by weight, preferably 5 to 100 parts by weight, of activecompound of group (6),

0.1 to 50 parts by weight, preferably 1 to 20 parts by weight, of activecompound of group (7),

0.11 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (8),

0.02 to 50 parts by weight, preferably 0.1 to 10 parts by weight, ofactive compound of group (9),

0.1 to 20 parts by weight, preferably 0.5 to 10 parts by weight, ofactive compound of group (10),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (11),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (12),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (13),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (14),

0.2 to 50 parts by weight, preferably 1 to 20 parts by weight, of activecompound of group (15),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (16),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (17),

1 to 150 parts by weight preferably 5 to 100 parts by weight, of activecompound of group (18),

0.1 to 150 parts by weight, preferably 1 to 100 parts by weight, ofactive compound of group (19),

0.02 to 50 parts by weight, preferably 0.2 to 10 parts by weight, ofactive compound of group (20),

0.05 to 20 parts by weight, preferably 0.1 to 10 parts by weight, ofactive compound of group (21),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (22),

0.1 to 50 parts by weight, preferably 0.2 to 20 parts by weight, ofactive compound of group (23),

0.02 to 50 parts by weight, preferably 0.04 to 10 parts by weight, ofactive compound of group (24) and/or

0.2 to 50 parts by weight, preferably 1 to 20 parts by weight, of activecompound of group (25),

are employed per part by weight of active compound of the formula (I).

The active compound combinations according to the invention have verygood fungicidal properties and can be employed for controllingphytopathogenic fungi, such as Plasmodiophoromycetes, Oomycetes,Chytridiomycetes, Zygomycetes, Ascomycetes, Basidiomycetes,Deuteromycetes, etc.

The active compound combinations according to the invention areparticularly suitable for controlling cereal diseases, such as Erysiphe,Puccinia and Fusarium, and for controlling diseases encountered inviticulture, such as Uncinula, Plasmopara and Botrytis, and furthermorein dicotyledonous crops for controlling powdery and downy mildew fungiand causative organisms of leaf spot.

The fact that the active compound combinations are well tolerated byplants at the concentrations required for controlling plant diseasespermits the treatment of above-ground parts of plants, of propagationstock and seeds, and of the soil. The active compound combinationsaccording to the invention can be employed for foliar application orelse as seed dressings.

The active compound combinations according to the invention can beconverted to the customary formulations, such as solutions, emulsions,suspensions, powders, foams, pastes, granules, aerosols andmicroencapsulations in polymeric substances and in coating compositionsfor seeds, and ULV formulations.

These formulations are produced in a known manner, for example by mixingthe active compounds or active compound combinations with extenders,that is liquid solvents, liquefied gases under pressure, and/or solidcarriers, optionally with the use of surfactants, that is emulsifiersand/or dispersants, and/or foam formers. If the extender used is water,it is also possible to use, for example, organic solvents as auxiliarysolvents. Essentially, suitable liquid solvents include: aromatics suchas xylene, toluene or alkylnaphthalenes, chlorinated aromatics orchlorinated aliphatic hydrocarbons such as chlorobenzenes,chloroethylenes or methylene chloride, aliphatic hydrocarbons such ascyclohexane or paraffins, for example petroleum fractions, alcohols suchas butanol or glycol and their ethers and esters, ketones such asacetone, methyl ethyl ketone, methyl isobutyl ketone or cyclohexanone,strongly polar solvents such as dimethylformamide and dimethylsulphoxide, or else water. Liquefied gaseous extenders or carriers areto be understood as meaning liquids which are gaseous at ambienttemperature and under atmospheric pressure, for example aerosolpropellants such as butane, propane, nitrogen and carbon dioxide.Suitable solid carriers are: for example ground natural minerals such askaolins, clays, talc, chalk, quartz, attapulgite, montmorillonite ordiatomaceous earth, and ground synthetic minerals such as finely dividedsilica, alumina and silicates. Suitable solid carriers for granules are:for example crushed and fractionated natural rocks such as calcite,marble, pumice, sepiolite and dolomite, or else synthetic granules ofinorganic and organic meals, and granules of organic material such assawdust, coconut shells, maize cobs and tobacco stalks. Suitableemulsifiers and/or foam formers are: for example nonionic and anionicemulsifiers, such as polyoxyethylene fatty acid esters, polyoxyethylenefatty alcohol ethers, for example alkylaryl polyglycol ethers,alkylsulphonates, alkyl sulphates, arylsulphonates, or else proteinhydrolysates. Suitable dispersants are: for example ligninsulphite wasteliquors and methylcellulose.

Tackifiers such as carboxymethylcellulose and natural and syntheticpolymers in the form of powders, granules or lattices, such as gumarabic, polyvinyl alcohol and polyvinyl acetate, or else naturalphospholipids such as cephalins and lecithins, and syntheticphospholipids can be used in the formulations. Other additives can bemineral and vegetable oils.

It is possible to use colourants such as inorganic pigment s, forexample iron oxide, titanium oxide and prussian blue, and organicdyestuffs such as alizarin dyestuffs, azo dyestuffs and metal phthaloanedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compounds, preferably between 0.5 and 90%.

In the formulations, the active compound combinations according to theinvention can be present as a mixture with other known active compoundssuch as fungicides, insecticides, acaricides and herbicides, and asmixtures with fertilizers or plant growth regulators.

The active compound combinations can be used as such, in the form oftheir formulations or as the use forms prepared therefrom, such asready-to-use solutions, emulsifiable concentrates, emulsions,suspensions, wettable powders, soluble powders and granules. They areused in the customary manner, for example by watering, spraying,atomizing, scattering, spreading, and as a powder for dry seedtreatment, a solution for seed treatment, a water-soluble powder forseed treatment, a water-soluble powder for slurry treatment, or byencrusting.

When using the active compound combinations according to the invention,the application rates can be varied within a relatively wide range,depending on the kind of application. In the treatment of parts ofplants, the application rates of the active compound combination aregenerally between 0.1 and 10,000 g/ha, preferably between 10 and 1000g/ha. In the treatment of seeds, the application rates of the activecompound combination are generally between 0.001 and 50 g per kilogramof seed, preferably between 0.01 and 10 g per kilogram of seed. In thetreatment of the soil, the application rates of the active compoundcombination are generally between 0.1 and 10,0009gha, preferably between1 and 5000 g/ha.

The good fungicidal activity of the active compound combinationsaccording to the invention is evident from the examples below. While theindividual active compounds exhibit weaknesses with regard to thefungicidal activity, the combinations have an activity which exceeds asimple addition of activities.

A synergistic effect of fungicides is always present when the fungicidalactivity of the active compound combinations exceeds the total of theactivities of the active compounds when applied individually.

The expected activity for a given combination of two active compoundscan be calculated as follows (cf. Colby, S. R, “Calculating Synergisticand Antagonistic Responses of Herbicide Combinations”, Weeds 5 (1967),20-22)

If

X is the efficacy when applying active compound A at an application rateof mg/ha,

Y is the efficacy when applying active compound B at an application rateof ng/ha, and

E is the efficacy when applying the active compounds A and B atapplication rates of m and n g/ha, then$E = {X + Y - \frac{X \cdot Y}{100}}$

The efficacy is calculated in %. 0% is an efficacy which corresponds tothat of the control, while an efficacy of 100% means that no infectionis observed.

If the actual fungicidal activity exceeds the calculated value, then theactivity of the combination is superadditive, i.e. a synergistic effectexists. In this case, the efficacy which was actually observed must begreater than the value for the expected efficacy (E) calculated from theabovementioned formula.

The examples that follow illustrate the invention.

EXAMPLE 1

Phytophthora Test (tomato)/Protective

Solvent: 47 parts by weight of acetone

Emulsifier: 3 parts by weight of allylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound or active compound combination is mixed with thestated amounts of solvent and emulsifier and the concentrate is dilutedwith water to the desired concentration, or a commercial formulation ofactive compound or active compound combination is diluted with water tothe desired concentration.

To test for protective activity, young plants are sprayed with theactive compound preparation at the stated application rate. After thespray coating has dried on, the plants are inoculated with an aqueousspore suspension of Phytophthora infestans. The plants are then placedin an incubation cabinet at about 20° C. and 100% relative atmospherichumidity.

Evaluation is carried out 3 days after the inoculation. 0% means anefficacy which corresponds to that of the control, while an efficacy of100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE 1 Phytophthora test (tomato)/protective Active compoundapplication rate Efficacy Active compound in g/ha in % Known:

1 0.2 65 14

1 0.2 76 37

2 0

2 26

2 17

2 58

2 12

2 36

1 0

1 0

0.2 51

0.2 0

1 27

0.2 0

0.2 0

0.2 0

0.2 0

1 0.2 0 0

0.2 24

0.2 0

0.2 0

0.2 0

0.2 0

0.2 5

5 0

1 0

0.2 6 According to the invention: found calc.*)

54 14

55 37

74 36

86 53

73 29

70 48

79 64

93 74

71 45

83 60

69 37

81 37

87 69

71 14

75 37

73 37

75 54

46 14

81 37

56 14

67 37

73 14

58 37

50 37

82 65

67 37

85 52

51 14

71 37

56 14

84 37

67 14

75 37

51 14

69 37

67 18

87 40

90 65

90 76

89 65

95 76

73 19

90 41 found = efficacy found calc. = efficacy calculated using the Colbyformula

EXAMPLE 2

Fusarium Nivale Test (triticale)/Seed Treatment

The active compounds are applied as dry seed dressings. These areprepared by extending the respective active compound or the activecompound combination with ground minerals to give a finely pulverulentmixture which ensures uniform distribution on the seed surface.

To dress the seed, the infected seed together with the seed dressing isshaken for 3 minutes in a sealed glass flask.

2×100 corns of triticale are sown at a depth of 1 cm in standard soiland cultivated in a greenhouse at a temperature of about 10° C. and arelative atmospheric humidity of about 95% in seed trays which receive alight regimen of 15 hours per day.

About 3 weeks after sowing, the plants are evaluated for symptoms. 0%means an efficacy which corresponds to that of the control, while anefficacy of 100% means that no infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE 2 Fusarium nivale test (triticale)/seed treatment Active compoundapplication rate in Active compound mg/kg of seed Efficacy in % Known:(Ia) 100 26 (Ib) 500 0 100 0 (XXII) 100 0 (IX) 500 0 (VIIc) 100 0 (IVb)100 3 Mixtures according to the invention: (Ia + VIIc) (1:1) 50 + 50 66(Ib + XXII) (1:1) 50 + 50 36 (Ib + IX) (1:1) 250 + 250 43 (Ib + VIIc)(1:1) 50 + 50 32 (Ib + IVb) (1:1) 50 + 50 75

EXAMPLE 3

Pythium sp. Test (pea) 1 Seed Treatment

The active compounds are applied as dry seed dressings. These areprepared by extending the respective active compound or the activecompound combination with ground minerals to give a finely pulverulentmixture which ensures uniform distribution on the seed surface.

To dress the seed, the infected seed together with the seed dressing isshaken for 3 minutes in a sealed glass flask.

21×50 corns of seed are sown at a depth of 2 cm in compost soilnaturally infected with phythium sp. and cultivated in a greenhouse at atemperature of about 20° C. in seed trays which receive a light regimenof 15 hours per day.

Evaluation is carried out after 14 days. 0% means an efficacy whichcorresponds to that of the control, while an efficacy of 100% means thatno infection is observed.

Active compounds, application rates and test results are shown in thetable below.

TABLE 3 Pythium sp. test (pea)/seed treatment Active compoundapplication rate in Active compound mg/kg of seed Efficacy in % Known:(Ia)  500 1 (Ib) 1000 4 (VIIc) 1000 8 (IVb) 1000 42  500 37 Mixturesaccording to the invention: (Ia + IVb) (1:1) 250 + 250 55 (Ib + VIIc)(1:1) 500 + 500 38 (Ib + IVb) (1:1) 500 + 500 59

What is claimed is:
 1. A fungicidal composition comprising synergisticfungicidally effective amounts of an active compound combinationcomprising (a) a halogeno-benzimidazole of the formula:

wherein Z is chlorine or bromine, (b) a compound of the formula

wherein the weight ratio of component (a) to component (b) is from1:0.02 to 1:20.
 2. The fungicidal composition of claim 1, wherein Z informula I is chlorine.
 3. The composition of claim 1 wherein the weightratio is 1:5.
 4. A method for controlling fungi comprising applying asynergistic fungicidally effective amount of an active compoundcombination according to claim 1 to the fungi and/or their habitat.